Herbicidal compositions

ABSTRACT

A herbicide combination comprising of components (A) and (B) exhibit synergistic herbicidal effects, where
     (A) is one or more herbicides selected from the group consisting of heteroaryloxy- and aryloxy-phenoxypropionic acids, their salts and esters and cyclohexanediones,
 
and
   (B) is one or more herbicides selected from the group consisting of
       (B1) herbicides which are selective in rice, mainly against mono-cotyledonous plants,   (B2) herbicides which are selective in rice, mainly against dicotyledonous harmful plants and cyperaceae,   (B3) herbicides which are selective in rice, mainly against cyperaceae and   (B4) herbicides which are selective in rice, mainly against mono-cotyledonous and dicotyledonous plants and cyperaceae.

The invention is in the field of crop protection compositions which canbe used against harmful plants in crops, preferably in rice, and whichcomprise, as herbicidally active compounds, a combination of at leasttwo herbicides, one herbicide component being selected from the groupconsisting of the herbicides of the type of the fatty acid biosynthesisinhibitors.

A number of compounds from the structure class of thearyloxyphenoxypropionic acids, cyclohexanediones and derivatives of theabovementioned compounds and their derivatives are known as herbicidesof the type of the fatty acid biosynthesis inhibitors. An advantage ofthese compounds is their activity against grasses, and a selective use,if appropriate in combination with safeners, is possible and utilizedeven in monocotyledonous crops.

The effectiveness of these herbicides against harmful plants in thecrops is at a high level; however, it depends in general on theapplication rate, the respective formulation, the harmful plants to becontrolled in each case or the spectrum of harmful plants, the climaticand soil conditions, etc. A further criterion is the duration of theaction, or the rate of degradation of the herbicide. Also to be takeninto account are, if appropriate, changes in the susceptibility ofharmful plants toward an active compound which may occur on prolongeduse or in geographical locations. Activity losses in individual plantscan only be compensated to a certain extent by higher application ratesof the herbicides, for example because this frequently decreases theselectivity of the herbicides, or an improvement in activity is notobserved, even at higher application rates. In some cases, it ispossible to improve the selectivity in crops by addition of safeners. Ingeneral, however, there is always a need for methods to achieve theherbicidal action with a lower application rate of active compounds. Alower application rate reduces not only the amount of an active compoundwhich is required for the application, but generally also reduces theamount of formulation auxiliaries required. Both reduce the economicexpense and improve the ecological compatibility of the herbicidetreatment. A method for improving the property profile of a herbicidemay consist in the combination of the active compound with one or moreother active compounds which contribute the desired additionalproperties. However, when two or more active compounds are applied incombination, it is not uncommon for phenomena of physical and biologicalincompatibility to occur, for example lack of stability of acoformulation, decomposition of an active compound or antagonism of theactive compounds. In contrast, what is desired are combinations ofactive compounds having a favorable activity profile, high stability andas synergistically enhanced an activity as possible which permits areduction of the application rate, compared with the individualapplication of the active compounds to be combined.

Surprisingly, it has now been found that active compounds from theabovementioned herbicide classes interact in a particularly favorablemanner in combination with certain structurally different herbicideswhen they are used against harmful plants in crops of rice. The useapplies preferably to crops of rice which are substantially tolerant tothe use of the herbicides, if appropriate with addition of safeners. Byintroducing tolerant or resistant varieties or lines of rice, inparticular transgenic varieties and lines of rice, the customary systemof weed control is supplemented by new active compounds which, per se,are nonselective in customary varieties of rice.

The combinations according to the invention are furthermore frequentlyalso suitable for controlling the same harmful plants in other crops.

The invention accordingly provides herbicide combinations having aneffective content of components (A) and (B), where

-   (A) is one or more herbicides selected from the group consisting of    heteroaryloxy- and aryloxy-phenoxypropionic acids, their salts and    esters and cyclohexanediones,    and-   (B) is one or more herbicides which are structurally different from    the herbicides (A) contained in each case, selected from the group    of the compounds consisting of-   (B1) herbicides which are selective in rice, mainly against    monocotyledonous plants,-   (B2) herbicides which are selective in rice, mainly against    dicotyledonous harmful plants and cyperaceae,-   (B3) herbicides which are selective in rice, mainly against    cyperaceae and-   (B4) herbicides which are selective in rice, mainly against    monocotyledonous and dicotyledonous harmful plants and cyperaceae.

The herbicide combinations according to the invention may contain othercomponents, for example other herbicides, insecticides, fungicides,acaricides, crop protection agents of a different type (for examplesafeners), plant growth regulators and/or additives and/or formulationauxiliaries which are customary in crop protection. Here, the componentscan be formulated jointly (ready-to-use formulation) and used, or theycan be formulated separately and used jointly, for example in the tankmix or in sequential application.

The synergistic effects are observed when the active compounds (A) and(B) are applied jointly; however, they can also frequently be observedwhen the active compounds are applied at different times (splitting). Itis also possible to apply the herbicides or the herbicide combinationsin a plurality of portions (sequential application), for example afterpre-emergence applications, followed by post-emergence applications orafter early post-emergence applications, followed by medium or latepost-emergence applications. Preference is given here to the joint oralmost simultaneous application of the active compounds of thecombination in question, if appropriate in a plurality of portions.However, it is also possible to apply the individual active compounds ofa combination at different times, which may be advantageous in theindividual case. It is also possible to integrate other crop protectionagents, such as fungicides, insecticides, acaricides, etc., and/orvarious auxiliaries, adjuvants and/or fertilizer applications, into thissystem application.

By the combined use of the herbicides (A) and (B), it is possible toachieve use properties which exceed what was to be expected based on theknown properties of the individual herbicides for their combination. Thesynergistic effects permit a reduction of the application rates of theindividual active compounds, a higher efficacy at the same applicationrate, the control of harmful plants which were as yet uncontrolled(gaps), an extension of the period of application and/or a reduction inthe number of individual applications required and—as a result for theuser—weed control systems which are more advantageous economically andecologically.

Suitable combination partners (A) are, for example, the compounds (A1)and (A2) below, which can in each case be employed on their own or incombination with one another (in most cases, the herbicides are referredto by the common name for the active compound, in accordance with thereference “The Pesticide Manual” 11th Ed., British Crop ProtectionCouncil 1997, abbreviated “PM”):

(A1) herbicides from the group of the (hetero)aryloxyphenoxypropionicacids and their derivatives, which are active against monocotyledonousharmful plants, mainly via the leaf, and which can be used selectivelyin rice, if appropriate in combination with suitable safeners, forexample

-   (A1.1) “fenoxaprop-P” and its esters, such as the ethyl ester    “fenoxaprop-P-ethyl” (see PM, pp. 519-520)    (═(R)-2-[4-(6-chlorobenzoxyzolyl-2-yloxy)phenoxy]propionic acid or    its ethyl ester), also in the use form of the racemate “fenoxaprop”    and its esters, such as the ethyl ester, and/or-   (A1.2) “quizalofop-P” and its esters, such as the ethyl or tefuryl    ester (see PM, pp. 1089-1092)    (═(R)-2-[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionic acid or its    ethyl ester or tetrahydrofurfuryl ester), also in the form of the    racemate “quizalofop” and its esters; cf. also, as specific ester,    “propaquizafop” (compound A1.3), and/or-   (A1.3) “propaquizafop” (PM, pp. 1021-1022), the    2-isopropylideneaminooxyethyl ester of quizalofop-P and/or-   (A1.4) “fluazifop-P” and its esters, such as the butyl ester (see    PM, pp. 556-557)    (═(R)-2-[4-(5-trifluoromethylpyrid-2-yloxy)phenoxy]propionic acid or    its butyl ester), also in the use form of the racemate “fluazifop”    and its esters, and/or-   (A1.5) “haloxyfop-P” and its esters, such as the methyl ester (see    PM, pp. 660-663)    (═(R)-2-[4-(3-chloro-5-trifluoromethylpyrid-2-yloxy)phenoxy]propionic    acid or its methyl ester), also in the use form of the racemate    “haloxyfop” and its esters, such as the methyl or the etotyl ester    and/or-   (A1.6) “cyhalofop” and its esters, such as the butyl ester (PM, pp.    297-298) (═(R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propionic acid    or its butyl ester) and/or-   (A1.7) “clodinafop” and its esters, such as the propargyl ester (PM,    pp. 251-252)    (═(R)-2-[4-(5-chloro-3-fluoropyrid-2-yloxy)phenoxy]propionic acid or    its propargyl ester).    (A2) Herbicides of the group of the cyclohexanediones which are    active against monocotyledonous harmful plants via the leaf and the    soil and which can be employed selectively in rice, for example-   (A2.1) “sethoxydim” (PM, pp. 1101-1103)    (═(RS)-(EZ)-2-(1-ethoxyiminobutyl)-5-[5-(ethylthio)propyl]-3-hydroxycyclohexen-2-enone)    and/or-   (A2.2) “cycloxydim” (PM, pp. 290-291)    (═(RS)-2-(1-ethoxyiminobutyl)-5-[5-(ethylthio)propyl]-3-hydroxy-5-thian-3-ylcyclohexen-2-enone)    and/or-   (A2.3) “clethodim” (PM, pp. 250-251)    (═(RS)-2-{(E)-1-[(E)-3-chloroallyloxyimino]propyl}-5-[2-(ethylthio)propyl]-3-hydroxycyclohexen-2-enone).-   (A2.4) “clefoxidim” or “BAS 625 H” (see AG Chem New Compound Review,    Vol. 17, 1999, p. 26, published by AGRANOVA)    (=2-[1-2-(4-chlorophenoxy)propoxyimino)butyl]-3-oxo-5-thion-3-ylcyclohex-1-enol).

The application rates of the herbicides (A) are known in principle andare, for the herbicides of type (A1), in the range from 5 g to 500 g ofactive substance per hectare and, for the herbicides of type (A2), inthe range from 10 g to 1000 g of active substance per hectare. In thecontext of the abovementioned application rates, the mixtures accordingto the invention require lower application rates of the particularactive compound, compared to the individual application.

Suitable combination partners (B) are, for example, the followingcompounds of the subgroups (B1) to (B4) which are different from thecompounds (A) (the herbicides are in most cases referred to by thecommon name, in accordance with the reference “The Pesticide Manual”11th Ed., British Crop Protection Council 1997, abbreviated “PM”):

(B1) Herbicides which are selective in rice, in particular againstmonocotyledonous harmful plants, are, for example, one or more compoundsselected from the group consisting of

-   (B1.1) butachlor (PM, pp. 159-160    (═N-(butoxymethyl)-2-chloro-N-(2,6-diethylphenyl)acetamide,-   (B1.2) butenachlor (PM, p. 1291)    (═N-(but-2-enyloxymethyl)-2-chloro-N-(2,6-diethylphenyl)acetamide,-   (B1.3) thenylchlor (PM, pp. 1182-1183)    (=2-chloro-N-(2,6-dimethylphenyl)-N-[(3-methoxy-2-thienyl)methyl]acetamide),-   (B1.4) pretilachlor (PM, pp. 995-996)    (=2-chloro-N-(2,6-diethylphenyl)-N-(propoxyethyl)acetamide,-   (B1.5) mefenacet (PM, pp. 779-781)    (=2-(1,3-benzthiazol-2-yloxy)-N-methylacetanilide,-   (B1.6) naproanilide (PM, pp. 865-866)    (═N-phenyl-2-(2-naphthyloxy)-propionamide,-   (B1.7) propanil (PM, pp. 1017-1019)    (═N-(3,4-dichlorophenyl)propanamide),-   (B1.8) etobenzanide (PM, pp. 492-493)    (═N-(2,3-dichlorophenyl)-4-(ethoxyphenoxy)benzamide,-   (B1.9) dimepiperate (PM, pp. 404-405) (═S-1-methyl-1-phenylethyl    piperidin-1-thiocarboxylate),-   (B1.10) molinate (PM, pp. 847-849) (═S-ethyl    azepan-1-thiocarboxylate),-   (B1.11) thiobencarb (benthiocarb) (PM, pp. 1192-1193)    (═S-4-chlorobenzyl diethyl thiocarbamate),-   (B1.12) pyributicarb (PM, pp. 1060-1061) (═O-3-tert-butylphenyl    6-methoxy-2-pyridyl(methyl)thiocarbamate,-   (B1.13) quinclorac (PM, pp. 1079-1080)    (=3,7-dichloroquinoline-8-carboxylic acid),-   (B1.14) sulcotrione (PM, pp. 1124-1125), i.e.    2-(2-chloro-4-mesyl-benzoyl)cyclohexane-1,3-dione,-   (B1.15) fentrazamid (BAY NBA 061)    (═N-cyclohexyl-N-ethyl-4-(2-chlorophenyl)-5-oxo-4,5-dihydrotetrazole-1-carboxamide),-   (B1.16) piperophos (PM, pp. 983-984)    (═S-2-methyl-1-piperidinylcarbonylmethyl O,O-dipropyl    dithiophosphate),-   (B1.17) JC-940 (“cumyluron”)    (=3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see    JP-A-60087254),-   (B1.18) dithiopyr (PM, pp. 442-443) (═S,S′-dimethyl    2-difluoromethyl-4-isobutyl-6-trifluoromethylpyridin-3,5-di(thiocarboxylate),-   (B1.19) bromobutide (PM, pp. 144-145)    (=2-bromo-3,3-dimethyl-N-(1-methyl-1-phenylethyl)butyramide),-   (B1.20) cinmethylin (PM, pp. 246-248) (=[(1RS, 2SR,    4SR)-1,4-epoxy-p-menth-2-yl) (2-methylbenzyl)ether) and-   (B1.21) cafenstrole (CH 900) (PM, pp. 173-174)    (═N,N-diethyl-3-mesitylsulfonyl-1H-1,2,4-triazol-1-carboxamide),    -   where in the case of the active compound (A1.2), (A1.3), (A1.4),        (A1.5), (A2.1), (A2.2) or (A2.3), it is also possible to use-   (B1.22) anilofos (PM, pp. 47-48)    (═S-4-chloro-N-isopropylcarbaniloylmethyl O,O-dimethyl    dithiophosphate),    as herbicidally active combination compound of the group (B1), alone    or in combination with the abovementioned active compounds, and    -   where in the case of the active compound (A1.1), it is also        possible to use-   (B1.24) cyhalofop, in particular its butyl ester, and-   (B1.25) clodinafop and esters, in particular its propargyl ester,    as herbicidally active combination compound of the group (B1), alone    or in combination with the abovementioned active compounds, and    -   where in the case of the active compound (A1.2) or (A1.3), it is        also possible to use-   (B1.24) cyhalofop and esters, in particular its butyl ester,-   (B1.25) clodinafop and esters, in particular its propargyl ester,-   (B1.26) fluazifop-(P) and its esters, in particular    fluazifop-P-butyl,-   (B1.27) haloxyfop-(P) and its esters, in particular    haloxyfop-(P)-methyl,-   (B1.28) sethoxydim,-   (61.29) cycloxydim,-   (B1.30) clethodim and-   (B1.31) clefoxidim    as herbicidally active combination compound of the group (B1), alone    or in combination with the abovementioned active compounds, and    -   where in the case of the active compound (A1.4) or (A1.5), it is        also possible to use-   (B1.24) cyhalofop and esters, in particular its butyl ester,-   (B1.25) clodinafop and esters, in particular its propargyl ester,-   (B1.28) sethoxydim,-   (B1.29) cycloxydim,-   (B1.30) clethodim and-   (B1.31) clefoxidim    as herbicidally active combination compound of the group (B1), alone    or in combination with the abovementioned active compounds, and    -   where in the case of the active compound (A1.7), it is also        possible to use-   (B1.28) sethoxydim,-   (B1.29) cycloxydim,-   (B1.30) clethodim and-   (B1.31) clefoxidim    as herbicidally active combination compound of the group (B1), alone    or in combination with the abovementioned active compounds, and    -   where in the case of the active compound (A2.1), (A2.2), (A2.3)        or (A2.4) it is also possible to use structurally different        herbicides selected from the group consisting of-   (B1.28) sethoxydim,-   (61.29) cycloxydim,-   (B1.30) clethodim and-   (B1.31) clefoxidim    as herbicidally active combination compound of the group (B1), alone    or in combination with the abovementioned active compounds.

Among the abovementioned combinations, preference is given to those inwhich herbicides from the group (A) are combined with those herbicidesfrom the group (B) which are not listed in the group (A).

Particular preference is given to herbicide combinations (A)+(B1)according to the invention which comprise the following activecompounds:

(A1.1)+(B1.1), (A1.1)+(B1.2), (A1.1)+(B1.3), (A1.1)+(B1.4),(A1.1)+(B1.5), (A1.1)+(B1.6), (A1)+(B1.7), (A1.1)+(B1.8), (A1.1)+(B1.9),(A1.1)+(B1.10), (A1.1)+(B1.11), (A1.1)+(B1.12), (A1.1)+(B1.13),(A1.1)+(B1.14), (A1.1)+(B1.15), (A1.1)+(B1.16), (A1.1)+(B1.17),(A1.1)+(B1.18), (A1.1)+(B1.19), (A1.1)+(B1.20) or (A1.1)+(B1.21) or else

(A1.1)+(B1.24) or (A1.1)+(B1.25).

In each case, the preferred compound (A1.1) is fenoxaprop-P-ethyl.

The active compounds which belong in each case to the same chemicalclass form, in the group (B1) and in the groups (B2) to (B4) illustratedfurther below, in each case preferred subgroups, because they areparticularly similar to one another in some use properties.

Thus, the abovementioned active compounds (B1.1) to (B1.8) are anilidesor chloroacetanilides which are active mainly against harmful grasses,for example annual grasses, and can be used in rice. Additionally,butachlor and pretilachlor also cover some broad-leaved weeds in rice,

naproanilide, propanil and etobenzanide have as activity spectrum, inaddition to grass-like species such as Echinochloa spp., Digitaria spp.,Setaria spp., Panicum spp., also broad-leaved weeds, such as Amaranthusspp.

The compounds (B1.9) to (B1.12) are thiocarbamates, with the emphasis onthe use against Echinochloa spp. in rice.

The compound (B1.13) belongs to the chemical class of thequinolinecarboxylic acids and is preferably used against weed grassessuch as Echinochloa spp. and other weeds in rice.

The compound (B1.14) is a benzoylcyclohexanedione which can be used notonly against weed grasses, but also against a broader spectrum of weedsin rice.

The compound (B1.17) from the tetrazole series is particularly suitablefor controlling weed grasses in rice.

The compounds (B1.16) and (B1.22) are organophosphorus compounds and areparticularly suitable for controlling annual grasses and seeds in rice.

The compound (B1.17) from the group of the ureas is suitable forcontrolling annual and perennial weed grasses in rice.

The compound (B1.18) from the pyridine series is suitable for useagainst annual grasses in rice.

The compound (B1.19) is particularly effective against weed grasses,sedges and some broad-leaved weeds in rice.

The compound (B1.20) is employed for controlling important weed grassesin rice.

The compound (B1.21) is a grass herbicide against annual harmful plantsin rice by the pre- and post-emergence method.

The compound (B1.22) is a grass herbicide against annual grasses andalso sedges in transplanted rice by the pre- and post-emergence method.

(B2) Herbicides which are selective in rice, mainly againstdicotyledonous harmful plants and cyperaceae, are, for example, one ormore compounds selected from the group consisting of

-   (B2.1) dicamba (PM, pp. 356-357), i.e. 3,6-dichloro-o-anisic acid    and its salts,-   (B2.2) carfentrazone and its esters, such as carfentrazone-ethyl    (PM, pp. 191-193)    (═(RS)-2-chloro-3-[2-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-4-fluorophenyl]propionic    acid and its esters, such as the ethyl ester),-   (B2.3) picloram (PM, pp. 977-979)    (═4-amino-3,5,6-trichloropyridine-2-carboxylic acid) and its salts,    such as the potassium salt,-   (B2.4) tritosulfuron (CAS Reg. No. 142469-14-5; (see AG Chem New    Compound Review, Vol. 17, 1999, p. 24, published by AGRANOVA))    (═N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]carbonyl]-2-(trifluoromethyl)benzenesulfonamide),    and    -   where in the case of the active compound (A1.3), (A1.4), (A1.5),        (A1.6), (A2.1), (A2.2), (A2.3) or (A2.4), it is also possible to        use-   (B2.5) acifluorfen (PM, pp. 12-14) and its salts, such as the sodium    salt (=5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid    or its salts, such as the Na salt),-   (B2.6) 2,4-D (PM, pp. 323-327) (=(2,4-dichlorophenoxy)acetic acid)    and its esters and salts,-   (B2.7) MCPA (PM, pp. 767-769) (=(4-chloro-2-methylphenoxy)acetic    acid) and its esters and salts,-   (B2.8) mecoprop or mecoprop-P (═(RS)— or    (R)-2-(4-chloro-o-tolyloxy)propionic acid) and its esters and salts    (PM, pp. 776-777),-   (B2.9) chlorimuron and its esters, such as chlorimuron-ethyl (PM,    pp. 217-218)    (=2-(4-chloro-2-methoxypyrimidin-2-ylcarbamoylsulfamoyl)benzoic acid    and its esters, such as the ethyl ester),-   (B2.10) triasulfuron (PM, pp. 1222-1224)    (=1-[2-(2-chloroethoxy)phenylsulfonyl]-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea)    and-   (B2.11) ioxynil (PM pp. 718-721) (=4-hydroxy-3,5-diiodobenzonitrile)    and its salts and esters    as herbicidally active combination compound of the group (B2), alone    or in combination with the abovementioned active compounds, and    -   where in the case of the active compound (A1.1), it is also        possible to use-   (B2.5) acifluorfen (PM, pp. 12-14) and its salts, such as the sodium    salt (=5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid    or its salts, such as the Na salt)    as herbicidally active combination compound of the group (82), alone    or in combination with the abovementioned active compounds.

Particular preference is given to herbicide combinations (A)+(B2)according to the invention which comprise the following activecompounds:

(A1.1)+(B2.1), (A1.1)+B2.2), (A1.1)+(B2.3), (A1.1)+(B2.4) or(A1.1)+(B2.5). The preferred compound (A1.1) is in each casefenoxaprop-P-ethyl.(B3) Herbicides which are selective in rice, mainly against cyperaceae,are, for example, one or more compounds selected from the groupconsisting of

-   (B3.1) triclopyr and its esters and salts    (=3,5,6-trichloro-2-pyridyloxyacetic acid and its salts and esters),-   (B3.2) benfuresate (PM, pp. 98-99)    (=2,3-dihydro-3,3-dimethylbenzofuran-5-yl ethanesulfonate) and-   (B3.3) daimuron (PM, p. 330)    (=1-(1-methyl-1-phenylethyl)-3-p-tolylurea,    -   where in the case of the active compound (A1.3), (A1.4), (A1.5),        (A1.6), (A2.1), (A2.2) or (A2.3) or (A2.4)-   (B3.4) bentazone (PM, pp. 109-111)    (=3-isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide) is    suitable.

Particular preference is given to herbicide combinations (A)+(B3.3)according to the invention which comprise the following activecompounds:

(A1.1)+(B3.1), (A1.1)+(B3.2) or (A1.1)+(B3.3). The preferred compound(A1.1) is in each case fenoxaprop-P-ethyl.(B4) Herbicides which are selective in rice, mainly againstmonocotyledonous and dicotyledonous harmful plants and cyperaceae, are,for example, one or more compounds selected from the group consisting of

-   (B4.1) pendimethalin (PM, pp. 937-939)    (N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine),-   (B4.2) clomazone (PM, pp. 256-257)    (=2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one),-   (B4.3) benzofenap (PM, pp. 111-112)    (=2-[4-(2,4-dichloro-m-toluoyl)-1,3-dimethylpyrazol-5-yloxy]-4′-methylacetophenone),-   (B4.4) pyrazolynate (PM, pp. 1049-1050)    (=4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl    toluene-4-sulfonate),-   (B4.5) pyrazoxfen (PM, pp. 1054-1055)    (=2-[4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yloxy]acetophenone),-   (B4.6) bispyribac, bispyribac-Na (KIH 2023) (PM, pp. 129-131)    (=sodium 2,6-bis-(4,6-dimethoxy-2-pyrimidin-2-yloxy)benzoate),-   (B4.7) pyriminobac (KIH 6127) (PM, pp. 1071-1073)    (=2-(4,6-dimethoxy-2-pyrimidinyloxy)-6-(1-methoxyiminoethyl)benzoic    acid) and its salts and esters, such as the methyl ester,-   (B4.8) oxadiazon (PM, pp. 905-907)    (=3-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2(3H)-one),-   (B4.9) oxadiargyl (PM, pp. 904-905)    (=5-tert-butyl-3-[2,4-dichloro-5-(prop-2-ynyloxy)phenyl]-1,3,4-oxadiazol-2(3H)-one),-   (B4.10) acetochlor (PM, pp. 10-12)    (=2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide),-   (B4.11) metolachlor (PM, pp. 833-834)    (=2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide),-   (B4.12) metosulam (PM, pp. 836-838)    (=2′,6′-dichloro-5,7-dimethoxy-3′-methyl[1,2,4]triazolo[1,5-a]pyrimidine-2-sulfonanilide),-   (B4.13) dalapon (PM, pp. 331-333) (=2,2-dichloropropionic acid) and    its salts, such as the sodium salt,-   (B4.14) cinosulfuron (PM, pp. 248-250)    (=1-(4,6-dimethoxy-1,3,5-triazin-2-yl)-3-[2-(2-methoxyethoxy)phenylsulfonyl]urea,-   (B4.15) pyrazosulfuron and its esters, such as pyrazosulfuron-ethyl    (PM, pp. 1052-1054)    (=5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1-methyl-pyrazol-4-carboxylic    acid) or its salts and esters, such as the ethyl ester,-   (B4.16) imazosulfuron (PM, pp. 703-704)    (=1-(2-chloroimidazol[1,2-a]pyridin-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea),-   (B4.17) cyclosulfamuron (PM, pp. 288-289)    (=1-(2-(cyclopropyl-carbonyl)phenylsulfamoyl]-3-(4,6-dimethoxypyrimidin-2-yl)urea),-   (B4.18) azimsulfuron (PM, pp. 63-65)    (=1-(4,6-dimethoxypyrimidin-2-yl)-3-[1-methyl-4-(2-methyl-2H-tetrazol-5-yl)-pyrazol-5-ylsulfonyl]urea),-   (B4.19) nicosulfuron (PM, pp. 877-879), i.e.    2-(4,6-dimethoxypyrimidin-2-yl)-3-(3-dimethylcarbamoyl-2-pyridylsulfonyl)urea    and its salts,-   (B4.20) prometryn (PM, pp. 1011-1013)    (N,N′-bis-(1-methylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine),-   (B4.21) simetryn (PM, pp. 1108-1109)    (N,N′-diethyl-6-(methylthio)-1,3,5-triazine-2,4-diamine),-   (B4.22) thiazopyr (PM, pp. 1185-1187) (=methyl    2-difluoromethyl-5-(4,5-dihydro-1,3-thiazol-2-yl)-4-isobutyl-6-trifluoromethylnicotinate),-   (B4.23) pentoxazone (KPP 314) (PM, pp.    942-943)(=3-(4-chloro-5-cyclopentyloxy-2-fluorophenyl)-5-isopropyliden-1,3-oxazolidine-2,4-dione),-   (B4.24) indanofan (PM, pp. 715)    (═(RS)-2-[2-(chlorophenyl)-2,3-epoxypropyl]-2-ethylindane-1,3-dione),-   (B4.25) pyribenzoxim (LGC 40863)    (=2,6-bis(4,6-dimethoxypyridin-2-yl)-1-N-(diphenylmethyl)iminooxycarbonyl]benzene),    introduced at the Brighton Crop Protection Conference Weeds 1997,-   (B4.26) oxaziclomefone    (=MY-100=3-[1-(3,5-dichlorophenyl)-1,1-dimethyl]-6-methyl-5-phenyl-2H,3H-1,3-oxazin-4-one    (from Rhone Poulenc)),-   (B4.27) fluthiamide (fenfenacet, BAY FOE 5043; PM, pp. 82-83)    (═N-(4-fluorophenyl)-N-(1-methylethyl)-2-[(trifluoromethyl)-1,3,4-thiadiazol-2-yloxy]acetamide),-   (B4.28) sulfentrazone (PM, pp. 1126-1127)    (═N-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1.2.4-triazol-1-yl)-phenyl]methanesulfonamide)    and-   (B4.29) esprocarb (PM, pp. 472-473) (═S-benzyl    1,2-dimethylpropyl-(ethyl)thiocarbamate),    -   where in the case of the active compound (A1.1), (A1.3), (A1.4),        (A1.5), (A1.6), (A2.1), (A2.2) or (A2.3), it is also possible to        use-   (B4.30) oxyfluorfen (PM, pp. 919-921)    (=2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene)    as herbicidaily active combination compound of the group (B4), alone    or in combination with the abovementioned active compounds, and    -   where in the case of the active compound (A1.2), (A1.3), (A1.4),        (A1.5), (A1.6), (A2.1), (A2.2) or (A2.3), it is also possible to        use-   (B4.31) bensulfuron-methyl (PM, pp. 104-105) (=methyl    2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]methyl]benzoate),-   (B4.32) ethoxysulfuron (PM, pp. 488-489)    (=1-(4,6-dimethoxypyrimidin-2-yl)-3-(2-ethoxyphenoxysulfonyl)urea,-   (B4.33) metsulfuron and its esters, such as the methyl ester (PM,    pp. 842-844)    (=2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]carbonyl]amino]sulfonyl]benzoic    acid and its esters, such as the methyl ester) and-   (B4.34) chlorsulfuron (PM, pp. 239-240)    (=1-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea)    as herbicidally active combination compound of the group (B4), alone    or in combination with the abovementioned active compounds.

Particular preference is given to herbicide combinations (A)+(B4)according to the invention which comprise the following activecompounds:

(A1.1)+(B4.1), (A1.1)+(B4.2), (A1.1)+(B4.3), (A1.1)+(B4.4),(A1.1)+(B4.5), (A1.1)+(B4.6), (A1.1)+(B4.7), (A1.1)+(B4.8),(A1.1)+(B4.9), (A1.1)+(B4.10), (A1.1)+(B4.11), (A1.1)+(B4.12),(A1.1)+(B4.13), (A1.1)+(B4.14), (A1.1)+(B4.15), (A1.1)+(B4.16),(A1.1)+(B4.17), (A1.1)+(B4.18), (A1.1)+(B4.19), (A1.1)+(B4.20),(A1.1)+(B4.21), (A1.1)+(B4.22), (A1.1)+(B4.23), (A1.1)+(B4.24),(A1.1)+(B4.25), (A1.1)+(B4.26), (A1.1)+(B4.27), (A1.1)+(B4.28),(A1.1)+(B4.29) or (A1.1)+(B4.30).In each case, the preferred compound (A1.1) is fenoxaprop-P-ethyl.

When the short form of the common name is used, this includes allcustomary derivatives, such as the esters and salts, in particular thecommercially available form or forms. In the case of sulfonylureas,salts include those which are formed by exchanging a hydrogen atom atthe sulfonamide group for a cation.

The application rates of the herbicides (B) are known in principle andare generally in the range from 1 g to 5000 g of AS/ha (g of AS/ha=g ofactive substance per hectare). Compounds (B) are preferably employed:

(B1) in amounts of from 10 to 4000, in particular 50-1000 g of AS/ha,(B2.1) to (B2.5) in amounts of from 5 to 1000, in particular 10-500 g ofAS/ha,(B2.6-B2.8) in amounts of from 100 to 3000, in particular 200-2000 g ofAS/ha;(B2.9-B2.10) in amounts of from 1 to 50, in particular 4-20 g of AS/ha;(B2.11) in amounts of from 1 to 2000, in particular 5 to 1000 g ofAS/ha;(B3) in amounts of from 50 to 2500, in particular 100-1000 g of AS/ha;(B4.1-B4.9) in amounts of from 50 to 5000, in particular 100-2500 g ofAS/ha;(B4.10-B4.13) in amounts of from 15 to 2000, in particular 30-1000 g ofAS/ha;(B4.14-B4.19) in amounts of from 2-80, in particular 4-40 g of AS/ha;(B4.20-B4.26) in amounts of from 15-2000, in particular 30-1000 g ofAS/ha;(B4.27-B4.29) in amounts of from 5-1000, in particular 10-500 g ofAS/ha;(B4.30) in amounts of from 15-2000, in particular 30-1000 g of AS/ha;(B4.31-B4.34) in amounts of from 2-80, in particular 4-40 g of AS/ha.

In the context of the abovementioned application rates, lowerapplication rates of the respective active compound are required in themixtures according to the invention, compared to the individualapplication. The ratios (A):(B) are, depending on the effectiveapplication rates, generally in the range from 1:200 to 200:1,preferably from 1:100 to 100:1, in particular in the range from 1:50 to50:1.

Preference is given to herbicide combinations of one or more compounds(A) with one or more structurally different compounds selected from thegroup consisting of (B1) or (B2) or (B3) or (B4).

Furthermore, preference is given to combinations of compounds (A) withone or more components (B) according to the scheme:

(A)+(B1)+(B2), (A)+(B1)+(B3), (A)+(B1)+(B4), (A)+(B2)+(B3),(A)+(B2)+(B4), (A)+(B3)+(B4), (A)+(B1)+(B2)+(B3), (A)+(B1)+(B2)+(B4),(A)+(B1)+(B3)+(B4).

Furthermore, the combinations according to the invention can be employedtogether with other active compounds, for example from the group of thesafeners, fungicides, insecticides and plant growth regulators, or fromthe group of the additives and formulation auxiliaries which arecustomary in crop protection.

Additives are, for example, fertilizers and colorants. Of particularimportance here are those combinations to which one or more other activecompounds of a different structure or safeners [active compounds (C)]are added, for example according to the scheme:

(A)+(B1)+(C), (A)+(B2)+(C) or (A)+(B3)+(C), (A)+(B4)+(C),(A)+(B1)+(B2)+(C), (A)+(B1)+(B3)+(C), (A)+(B1)+(B4)+(C),(A)+(B2)+(B3)+(C), (A)+(B2)+(B4)+(C), (A)+(B3)+(B4)+(C),(A)+(B1)+(B2)+B3)+(C), (A)+(B1)+(B2)+(B4)+(C), (A)+(B1)+(B3)+(B4)+(C),(A)+(B2)+(B3)+(B4)+(C) or (A)+(B1)+(B2)+(B3)+(B4)+(C).

For combinations of the last-mentioned kind with three or more activecompounds, the preferred conditions explained below in particular fortwo-component combinations according to the invention primarily applylikewise if they comprise the two-compound combinations according to theinvention, and with respect to the two-component combination inquestion.

In some cases, even combinations of different active compounds fromgroup (A) are synergistic, so that, based on these two-compoundcombinations, it is possible to obtain particularly favorablethree-compound combinations with additional synergistic effects.

The active compounds (A) are suitable for controlling the weed spectrumin rice crops, for example of transplanted or sown rice. Moreover, theycan, if appropriate, be employed for controlling harmful plants in othercrops, for example in economically important crops, such as cereals(wheat, barley, rye, maize), sugarbeet, sugar cane, rapeseed, cotton andsoybeans. When using the active compounds (A) and (B) in crops such asrice crops, it is advantageous, depending on the crop, to apply asafener above certain application rates to reduce or avoid damage to thecrop plant. The following groups of compounds are, for example, suitableas safeners for the abovementioned herbicidally active compounds (A):

-   a) Compounds of the type of dichlorophenylpyrazoline-3-carboxylic    acid, preferably compounds such as ethyl    1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate    (S1-1) (“mefenpyr-diethyl”, PM, pp. 781-782), and related compounds,    as described in WO 91/07874,-   b) Derivatives of dichlorophenylpyrazole carboxylic acid, preferably    compounds such as ethyl    1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl    1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carbooxylate (S1-3),    ethyl    1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate    (S1-4), ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate    (S1-5) and related compounds as described in EP-A-333 131 and    EP-A-269 806.-   c) Compounds of the type of the triazolecarboxylic acids, preferably    compounds such as fenchlorazole(ethyl ester), i.e. ethyl    1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate    (S1-6) and related compounds as described in EP-A-174 562 and    EP-A-346 620.-   d) Compounds of the type of the 5-benzyl- or    5-phenyl-2-isoxazoline-3-carboxylic acid, or the    5,5-diphenyl-2-isoxazoline-3-carboxylic acid, preferably compounds    such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate    (S1-7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-8) and    related compounds, as described in WO 91/08202, or ethyl    5,5-diphenyl-2-isoxazolinecarboxylate (S1-9) (“isoxadifen-ethyl”) or    its -n-propyl ester (S1-10) or ethyl    5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-11), as    described in the German patent application (WO-A-95/07897).-   e) Compounds of the type of the 8-quinolineoxyacetic acid (S2),    preferably 1-methylhex-1-yl (5-chloro-8-quinolineoxy)acetate (common    name “cloquintocet-mexyl” (S2-1) (see PM, pp. 263-264)    1,3-dimethylbut-1-yl (5-chloro-8-quinolineoxy)acetate (S2-2),    4-allyloxybutyl (5-chloro-8-quinolineoxy)acetate (S2-3),    1-allyloxyprop-2-yl (5-chloro-8-quinolineoxy)acetate (S2-4), ethyl    (5-chloro-8-quinolineoxy)acetate (S2-5), methyl    (5-chloro-8-quinolineoxy)acetate (S2-6), allyl    (5-chloro-8-quinolineoxy)acetate (S2-7),    2-(2-propylideneiminoxy)-1-ethyl (5-chloro-8-quinolineoxy)acetate    (S2-8), 2-oxoprop-1-yl (5-chloro-8-quinolineoxy)acetate (S2-9) and    related compounds, as described in EP-A-86 750, EP-A-94 349 and    EP-A-191 736 or EP-A-0 492 366.-   f) Compounds of the type of the (5-chloro-8-quinolineoxy)malonic    acid, preferably compounds such as diethyl    (5-chloro-8-quinolineoxy)malonate, diallyl    (5-chloro-8-quinolineoxy)malonate, methyl ethyl    (5-chloro-8-quinolineoxy)malonate and related compounds, as    described in EP-A-0 582 198.-   g) Active compounds of the type of the phenoxyacetic or -propionic    acid derivatives or the aromatic carboxylic acids, such as, for    example, 2,4-dichlorophenoxyacetic acid (esters) (2,4-D),    4-chloro-2-methylphenoxypropionic esters (Mecoprop), MCPA or    3,6-dichloro-2-methoxybenzoic acid (esters) (Dicamba).-   The abovementioned safeners are in many cases also suitable for    active compounds of group (B). Moreover, the following safeners are    suitable for the herbicide combinations according to the invention    in rice and other cereal crops, such as for example, wheat, maize,    millet, etc.:-   h) Active compounds of the type of the pyrimidines, which are used    as soil-acting safeners in rice, such as, for example,    -   “fenclorim” (PM, pp. 512-511)        (=4,6-dichloro-2-phenylpyrimidine), which is known as safener        for pretilachlor in sown rice,-   i) Active compounds of the type of the pyrimidines, which are used    as soil-acting safeners in rice, such as, for example,    -   “fenclorim” (PM, pp. 512-511)        (=4,6-dichloro-2-phenylpyrimidine), which is known as safener        for damage caused by pretilachlor in sown rice-   j) Active compounds of the type of the dichloroacetamides, which are    frequently used as pre-emergent safeners (soil-acting safeners),    such as, for example,    -   “dichlormid” (PM, pp. 363-364)        (═N,N-diallyl-2,2-dichloroacetamide),    -   “R-29148” (=3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine        from Stauffer),    -   “benoxacor” (PM, pp. 102-103)        (=4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine),    -   “PPG-1292”        (═N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide from        PPG Industries),    -   “DK-24”        (═N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide from        Sagro-Chem),    -   “AD-67” or “MON 4660”        (=3-dichloroacetyl-1-oxa-3-aza-spiro[4,5]decane from Nitrokemia        or Monsanto),    -   “diclonon” or “BAS145138” or “LAB145138”        (=3-dichloroacetyl-2,5,5-trimethyl-1,3-diazabicyclo[4.3.0]nonane        from BASF) and    -   “furilazol” or “MON 13900” (see PM, 637-638)        (═(RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine)-   k) Active compounds of the type of the dichloroacetone derivatives,    such as, for example,    -   “MG 191” (CAS-Reg. No. 96420-72-3)        (=2-dichloromethyl-2-methyl-1,3-dioxolane from Nitrokemia),        which is known as safener for maize,-   l) Active compounds of the type of the oxyimino compounds, which are    known as seed dressings, such as, for example,    -   “oxabetrinil” (PM, pp. 902-903)        (═(Z)-1,3-dioxolan-2-ylmethoxy-imino(phenyl)acetonitrile), which        is known as seed dressing safener for millet against metolachlor        damage,    -   “fluxofenim” (PM, pp. 613-614)        (=1-(4-chlorophenyl)-2,2,2-trifluoro-1′ ethanone        O-(1,3-dioxolan-2-ylmethyl)oxime), which is known as seed        dressing safener for millet against metolachlor damage,    -   “cyometrinil” or “-CGA-43089” (PM, p. 1304)        (═(Z)-Cyanomethoxyimino(phenyl)acetonitrile), which is known as        seed dressing safener for millet against metolachlor damage,-   m) Active compounds of the type of the thiazolecarboxylic esters,    which are known as seed dressings, such as, for example,    -   “flurazol” (PM, pp. 590-591) (=benzyl        2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate), which is        known as seed dressing safener for millet against alachlor and        metolachlor damage,-   n) Active compounds of the type of the naphthalenedicarboxylic acid    derivatives, whch are known as seed dressings, such as, for example,    -   “naphthalic anhydride” (PM, p. 1342)        (=1,8-naphthalenedicarboxylic anhydride), which is known as seed        dressing safener for maize against thiocarbamate herbicide        damage,-   o) Active compounds of the type of the chromanacetic acid    derivatives, such as, for example,    -   “CL 304415” (CAS-Reg. No. 31541-57-8)        (=2-(4-carboxychroman-4-yl)acetic acid from American Cyanamid),        which is known as safener for maize against imidazolinone        damage,-   p) Active compounds which, in addition to a herbidical action    against harmful plants, also have safener action in crop plants such    as rice, such as, for example,    -   “dimepiperate” or “MY-93” (PM, pp. 404-405)        (═S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate), which        is known as safener for rice against herbicide molinate damage,    -   “daimuron” or “SK 23” (PM, p. 330)        (=1-(1-methyl-1-phenylethyl)-3-p-tolylurea), which is known as        safener for rice against herbicide imazosulfuron damage,    -   “cumyluron”=“JC-940”        (=3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see        JP-A-60087254), which is known as safener for rice against        damage by some herbicides,    -   “methoxyphenon” or “NK 049”        (=3,3′-dimethyl-4-methoxy-benzophenone), which is known as        safener for rice against damage by some herbicides,    -   “CSB” (=1-bromo-4-(chloromethylsulfonyl)benzene) (CAS-Reg. No.        54091-06-4 from Kumiai), which is known as safener against        damage by some herbicides in rice.

Among the abovementioned safeners, (S1-1), (S1-9) and (S2-1), inparticular (S1-9), are of particular interest.

Some of the safeners are already mentioned above as herbicides andconsequently show, in addition to the herbicidal action against harmfulplants, also protective action in the case of the crop plants.

The invention furthermore provides the following specific two-compoundand multi-compound combinations with herbicides and/or safeners:

Active compound fenoxaprop (A1.1)+safener (S1-9)+thiazopyrActive compound fenoxaprop (A1.1)+safener (S1-9)+clomazoneActive compound fenoxaprop (A1.1)+safener (S1-9)+benthiocarbActive compound fenoxaprop (A1.1)+safener (S1-9)+butachlorActive compound fenoxaprop (A1.1)+safener (S1-9)+quinchloracActive compound fenoxaprop (A1.1)+safener (S1-9)+pendimethalinActive compound fenoxaprop (A1.1)+safener (S1-9)+oxadiargylActive compound fenoxaprop (A1.1)+safener (S1-9)+oxadiazonActive compound fenoxaprop (A1.1)+safener (S1-9)+cafenstrolActive compound fenoxaprop (A1.1)+safener (S1-9)+bispyribacActive compound fenoxaprop (A1.1)+safener (S1-9)+metosulamActive compound fenoxaprop (A1.1)+safener (S1-9)+carflutrazonActive compound fenoxaprop (A1.1)+safener (S1-9)+ethoxysulfuronActive compound fenoxaprop (A1.1)+ethoxysulfuron+anilofosActive compound fenoxaprop (A1.1)+ethoxysulfuron+quinchloracActive compound fenoxaprop (A1.1)+ethoxysulfuron+molinateActive compound fenoxaprop (A1.1)+bensulfuron-methyl+quinchloracActive compound fenoxaprop (A1.1)+bensulfuron-methyl+molinate

The abovementioned multi-compound combinations have synergies withrespect to the herbicidal action and selectivity and a favorable actionwith respect to the weed spectrum. Instead of the safener (S1-9) othersafeners can offen likewise be applied, preferably the safeners of theabove-mentioned groups a) through e).

The combinations according to the invention (=herbicidal compositions)have excellent herbicidal activity against a broad spectrum ofeconomically important mono- and dicotyledonous harmful plants, asencountered, preferably, in crops of rice. The active compounds also actefficiently on perennial weeds which produce shoots from rhizomes, rootstocks or other perennial organs and which are difficult to control. Inthis context, it is immaterial whether the substances are appliedpre-sowing, pre-emergence or post-emergence. Preference is given to theapplication by the post-emergence method or the earlypost-sowing/pre-emergence method.

Specifically, examples may be mentioned of some representatives of themonocotyledonous and dicotyledonous weed flora which can be controlledby the compounds according to the invention, without these being arestriction to certain species.

Among the monocotyledonous weed species, the active compounds actefficiently against, for example, Echinochloa spp., Brachiaria spp.,Leptochloa spp. and Digitaria spp., but also against Panicum spp.,Agropyron spp., wild cereal forms and Sorghum spp., Setaria spp.,Alopecurus spp., Avena spp., Apera spica venti, Lolium spp., Phalarisspp. Cynodon spp., Poa spp. and Cyperus species and Imperata.

In the case of the dicotyledonous weed species, the spectrum of actionextends to species such as, for example, Amaranthus spp., Sphenocleaspp., Heteranthera spp., Eleocharis spp., Ipomoea spp., Eschynomenaspp., Sesbania spp. and Cyperrus spp., but also Polygonum spp., Xanthiumspp., Equisetum, Chenopodium spp., Abutilon spp., Anthemis spp., Lamiumspp., Matricaria spp., Stellaria spp., Kochia spp., Viola spp., Daturaspp., Chrysanthemum spp., Thlaspi spp., Pharbitis spp., Sida spp.,Sinapis spp., Cupsella spp., Ambrosia spp., Galium spp., Emex spp.,Lamium spp., Papaver spp., Solanum spp., Cirsium spp., Veronica spp.,Convolvulus spp., Rumex and Artemisia.

If the compounds according to the invention are applied to the soilsurface prior to germination, then the weed seedlings are eitherprevented completely from emerging, or the weeds grow until they havereached the cotyledon stage but then their growth stops, and,eventually, after three to four weeks have elapsed, they die completely.

If the active compounds are applied post-emergence to the green parts ofthe plants, growth also stops drastically a very short time after thetreatment and the weed plants remain at the developmental stage of thepoint in time of application, or they die completely after a certaintime, so that in this manner competition by the weeds, which is harmfulto the crop plants, is eliminated at a very early point in time and in asustained manner.

The herbicidal compositions according to the invention have a rapid andlong-lasting herbicidal action. The shower resistance of the activecompounds in the combinations according to the invention is generallyfavorable. It is a particular advantage that the effective dosages ofcompounds (A) and (B) used in the combinations can be adjusted to such alow level, that their soil action is optimally low. Thus, it is not onlypossible to use them in sensitive crops, but groundwater contaminationsare virtually avoided. By using the active compound combinationaccording to the invention, it is possible to reduce the requiredapplication rate of the active compounds considerably.

When herbicides of type (A)+(B) are applied jointly, super additive(=synergistic) effects are observed. Here, the activity in thecombinations is stronger than the expected sum of the activities of theindividual herbicides used. The synergistic effects permit a reductionof the application rate, the control of a broader spectrum ofbroad-leaved weeds and weed grasses, a more rapid onset of theherbicidal action, a longer duration of action, a better control of theharmful plants with only one or a few applications and a widening of thepossible period of use. In some cases, the use of compositions alsoreduces the amount of harmful ingredients, such as nitrogen or oleicacid, and their incorporation into the soil.

The abovementioned properties and advantages are needed in practicalcontrol of weeds to keep agricultural crops free of undesirablecompeting plants and thus to secure and/or increase the quality andquantity of the yields. With respect to the described properties, theprior art is considerably surpassed by these novel combinations.

Although the compounds according to the invention have an excellentherbicidal activity against monocotyledonous and dicotyledonous weeds,the crop plants are not damaged at all, or only to a negligible extent.

In addition, the substances according to the invention have outstandinggrowth-regulating properties in crop plants. They engage in the plantmetabolism in a regulating manner and can thus be employed for thetargeted control of plant constituents and for facilitating harvesting,for example by provoking desiccation and stunted growth. Furthermore,they are also suitable for generally regulating and inhibitingundesirable vegetative growth, without destroying the plants in theprocess. Inhibition of vegetative growth plays an important role in manymonocotyledonous and dicotyledonous crops because lodging can be reducedhereby, or prevented completely.

Owing to their herbicidal and plant growth-regulatory properties, thecompounds can be employed for controlling harmful plants in known cropsor in still to be developed tolerant or genetically engineered plants.The transgenic plants generally have particularly advantageousproperties, in addition to resistance to the substances according to theinvention, for example resistance to plant diseases or causativeorganisms of plant diseases, such as certain insects or microorganismssuch as fungi, bacteria or viruses. Other particular properties relate,for example, to the quantity, quality, storage-stability, compositionand to specific ingredients of the harvested product. Thus, transgenicplants having an increased starch content or a modified quality of thestarch or those having a different fatty acid composition of theharvested product are known.

Conventional ways for preparing novel plants which have modifiedproperties compared to known plants comprise, for example, traditionalbreeding methods and the generation of mutants. Alternatively, novelplants having modified properties can be generated with the aid ofgenetic engineering methods (see, for example, EP-A 0 221 044, EP-A 0131 624). For example, there have been described several cases of

-   -   genetically engineered changes in crop plants in order to modify        the starch synthesized in the plants (for example WO 92/11376,        WO 92/14827, WO 91/19806),    -   transgenic crop plants which are resistant to other herbicides,        for example sulfonylureas (EP-A 0 257 993, U.S. Pat. No.        5,013,659),    -   transgenic crop plants having the ability to produce Bacillus        thuringiensis toxins (Bt toxins) which impart resistance to        certain pests to the plants (EP-A 0 142 924, EP-A 0 193 259),    -   transgenic crop plants having a modified fatty acid composition        (WO 91/13972).

Numerous molecular biological techniques which allow the preparation ofnovel transgenic plants having modified properties are known inprinciple; see, for example. Sambrook et al., 1989, Molecular Cloning, ALaboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, ColdSpring Harbor, N.Y.; or Winnacker “Gene und Klone” [Genes and Clones],VCH Weinheim, 2nd edition 1996, or Christou, “Trends in Plant Science” 1(1996) 423-431). In order to carry out such genetic engineeringmanipulations, it is possible to introduce nucleic acid molecules intoplasmids which allow a mutagenesis or a change in the sequence to occurby recombination of DNA sequences. Using the abovementioned standardprocesses it is possible, for example, to exchange bases, to removepartial sequences or to add natural or synthetic sequences. To link theDNA fragments with each other, it is possible to attach adaptors orlinkers to the fragments.

Plant cells having a reduced activity of a gene product can be prepared,for example, by expressing at least one appropriate antisense-RNA, asense-RNA to achieve a cosuppression effect, or by expressing at leastone appropriately constructed ribozyme which specifically cleavestranscripts of the abovementioned gene product.

To this end it is possible to employ both DNA molecules which comprisethe entire coding sequence of a gene product including any flankingsequences that may be present, and DNA molecules which comprise onlyparts of the coding sequence, it being necessary for these parts to belong enough to cause an antisense effect in the cells. It is alsopossible to use DNA sequences which have a high degree of homology tothe coding sequences of a gene product but which are not entirelyidentical.

When expressing nucleic acid molecules in plants, the synthesizedprotein can be localized in any desired compartment of the plant cells.However, to achieve localization in a certain compartment, it is, forexample, possible to link the coding region with DNA sequences whichensure localization in a certain compartment. Such sequences are knownto the person skilled in the art (see, for example, Braun et al., EMBOJ. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85(1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).

The transgenic plant cells can be regenerated to whole plants usingknown techniques. The transgenic plants can in principle be plants ofany desired plant species, i.e. both monocotyledonous and dicotyledonousplants. In this manner, it is possible to obtain transgenic plants whichhave modified properties by overexpression, suppression or inhibition ofhomologous (=natural) genes or gene sequences or by expression ofheterologous (=foreign) genes or gene sequences.

The invention therefore also provides a method for controllingundesirable vegetation, preferably in crops, which comprises applyingone or more herbicides of type (A) with one or more herbicides of type(B) onto the harmful plants, parts thereof or onto the area undercultivation.

The invention also provides the use of the novel combinations ofcompounds (A)+(B) for controlling harmful plants, preferably in crops.

The active compound combinations according to the invention can bepresent both as mixed formulations of the two components, if appropriatewith other active compounds, additives and/or customary formulationauxiliaries, which are then applied in a customary manner diluted withwater, or be prepared as so-called tank mixes by joint dilution of theseparately formulated or partially separately formulated components withwater.

The compounds (A) and (B) or their combinations can be formulated invarious ways depending on the prevailing biological and/orchemico-physical parameters. Examples of suitable formulation optionsare: wettable powders (WP), emulsifiable concentrates (EC), aqueoussolutions (SL) emulsions (EW), such as oil-in-water and water-in-oilemulsions, sprayable solutions or emulsions, oil- or water-baseddispersions, suspoemulsions, dusts (DP), seed-dressing compositions,granules for broadcasting and soil application, or water-dispersiblegranules (WG), ULV formulations, microcapsules or waxes.

The individual formulation types are known in principle and aredescribed, for example, in Winnacker-Küchler, “Chemische Technologie”[Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th. Edition1986; van Valkenburg, “Pesticides Formulations”, Marcel Dekker, N.Y.,1973; K Martens, “Spray Drying Handbook”, 3rd Ed. 1979, G. Goodwin Ltd.London.

The necessary formulation auxiliaries, such as inert materials,surfactants, solvents and other additives, are likewise known and aredescribed, for example, in Watkins, “Handbook of Insecticide DustDiluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J., H. v.Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley &Sons, N.Y.; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y.1950; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp.,Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface ActiveAgents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt,“Grenzflächenaktive Äthylenoxidaddukte” [Surface-active ethylene oxideadducts], Wiss. Verlagsgesellschoft, Stuttgart 1976; Winnacker-Küchler,“Chemische Technologie” [Chemical Technology], Volume 7, C. HauserVerlag Munich, 4th Edition 1986.

Based on these formulations it is also possible to produce combinationswith other pesticidally active substances, such as other herbicides,fungicides or insecticides, and also with safeners, fertilizers and/orgrowth regulators, for example in the form of a ready-mix or tank mix.

Wettable powders are preparations which are uniformly dispersible inwater and which contain, in addition to the active compound and as wellas a diluent or inert substance, surfactants of ionic or nonionic type(wetting agents, dispersants), for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines,alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium2,2′-dinaphthylmethane-6,6′-disulfonate, sodiumdibutylnaphthalene-sulfonate or else sodium oleoylmethyltaurinate.

Emulsifiable concentrates are prepared by dissolving the active compoundin an organic solvent, for example butanol, cyclohexanone,dimethylformamide, xylene or else relatively high-boiling aromaticcompounds or hydrocarbons with the addition of one or more surfactantsof ionic or nonionic type (emulsifiers). Examples of emulsifiers whichcan be used are calcium alkylarylsulfonates, such as Cadodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acidpolyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycolethers, propylene oxide-ethylene oxide condensation products, alkylpolyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fattyacid esters or polyoxyethylene sorbitan esters.

Dusts are obtained by grinding the active compound with finely dividedsolid substances, for example talc, natural clays, such as kaolin,bentonite and pyrophyllite, or diatomaceous earth.

Granules can be prepared either by spraying the active compound ontoadsorptive, granulated inert material or by applying active-compoundconcentrates to the surface of carriers such as sand, kaolinites orgranulated inert material, by means of adhesive binders, for examplepolyvinyl alcohol, sodium polyacrylate or else mineral oils. Suitableactive compounds can also be granulated in the manner which is customaryfor the preparation of fertilizer granules, if desired as a mixture withfertilizers.

Water-dispersible granules are generally prepared by processes such asspray-drying, fluidized-bed granulation, disk granulation, mixing usinghigh-speed mixers, and extrusion without solid inert material.

The agrochemical formulations generally contain from 0.1 to 99% byweight, in particular from 2 to 95% by weight, of active compounds oftypes A and/or B, the following concentrations being customary,depending on the type of formulations:

In wettable powders the concentration of active compound is, forexample, from about 10 to 95% by weight, the remainder to 100% by weightconsisting of customary formulation constituents. In emulsifiableconcentrates the concentration of active compound can be, for example,from 5 to 80% by weight.Formulations in the form of dusts usually contain from 5 to 20% byweight of active compound, while sprayable solutions contain from about0.2 to 25% by weight of active compound.In the case of granules, such as dispersible granules, the content ofactive compound depends partly on whether the active compound is inliquid or solid form and on the granulation auxiliaries and fillers thatare used. In water-dispersible granules the content is generally between10 and 90% by weight.

In addition, said formulations of active compound may comprise thetackifiers, wetting agents, dispersants, emulsifiers, preservatives,antifreeze agents and solvents, fillers, colorants and carriers,antifoams, evaporation inhibitors and pH and viscosity regulators whichare customary in each case.

For use, the formulations, which are in commercially available form,are, if appropriate, diluted in a customary manner, for example usingwater in the case of wettable powders, emulsifiable concentrates,dispersions and water-dispersible granules. Preparations in the form ofdusts, soil granules, granules for spreading and sprayable solutions areconventionally not diluted any further with other inert substances priorto use.

The active compounds can be applied to the plants, parts of the plants,seeds of the plants or the area under cultivation (tilled soil),preferably to the green plants and parts of the plants and, if desired,additionally to the tilled soil.

A possible use is the joint application of the active compounds in theform of tank mixes, where the concentrated formulations of theindividual active substances, in the form of their optimal formulations,are mixed jointly with water in the tank, and the spray mixture obtainedis applied.

A joint herbicidal formulation of the combination according to theinvention of the active compounds (A) and (B) has the advantage that itcan be applied more easily because the amounts of the components havealready been adjusted to one another in the correct ratio. Moreover, theauxiliaries of the formulation can be selected to suit each other in thebest possible way, while a tank mix of various formulations may resultin undesirable combinations of auxiliaries.

A. GENERAL FORMULATION EXAMPLES

-   a) A dust is obtained by mixing 10 parts by weight of an active    compound/active compound mixture and 90 parts by weight of talc as    inert substance and comminuting the mixture in a hammer mill.-   b) A wettable powder which is readily dispersible in water is    obtained by mixing 25 parts by weight of an active compound/active    compound mixture, 64 parts by weight of kaolin-containing quartz as    inert substance, 10 parts by weight of potassium lignosulfonate and    1 part by weight of sodium oleoylmethyltaurinate as wetting agent    and dispersant, and grinding the mixture in a pinned-disk mill.-   c) A dispersion concentrate which is readily dispersible in water is    obtained by mixing 20 parts by weight of an active compound/active    compound mixture with 6 parts by weight of alkylphenol polyglycol    ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol    ether (8 EO) and 71 parts by weight of paraffinic mineral oil    (boiling range for example approximately 255 to 277° C.) and    grinding the mixture in a ball mill to a fineness of below 5    microns.-   d) An emulsifiable concentrate is obtained from 15 parts by weight    of an active compound/active compound mixture, 75 parts by weight of    cyclohexanone as solvent and 10 parts by weight of ethoxylated    nonylphenol as emulsifier.-   e) Water-dispersible granules are obtained by mixing    -   75 parts by weight of an active compound/active compound        mixture,    -   10 parts by weight of calcium lignosulfonate,    -   5 parts by weight of sodium lauryl sulfate,    -   3 parts by weight of polyvinyl alcohol and    -   7 parts by weight of kaolin,    -   grinding the mixture in a pinned-disk mill and granulating the        powder in a fluidized bed by spraying on water as granulation        liquid.-   f) Water-dispersible granules are also obtained by homogenizing and    precomminuting, in a colloid mill,    -   25 parts by weight of an active compound/active compound        mixture,    -   5 parts by weight of sodium        2,2′-dinaphthylmethane-6,6′-disulfonate,    -   2 parts by weight of sodium oleoylmethyltaurinate,    -   1 part by weight of polyvinyl alcohol,    -   17 parts by weight of calcium carbonate and    -   50 parts by weight of water,    -   subsequently grinding the mixture in a bead mill and atomizing        and drying the resulting suspension in a spray tower by means of        a single-substance nozzle.

B. BIOLOGICAL EXAMPLES 1. Pre-Emergence Effect on Weeds

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weedplants are placed in sandy loam soil in pots and covered with soil. Thecompositions, formulated in the form of concentrated aqueous solutions,wettable powders or emulsion concentrates, are then applied to thesurface of the soil cover as aqueous solution, suspension or emulsion atan application rate of 600 to 800 I of water/ha (converted), in variousdosages. After the treatment, the pots are placed in a greenhouse andkept under good growth conditions for the weeds. After the test plantshave emerged, the damage to the plants or the negative effects on theemergence is scored visually after a test period of 3 to 4 weeks bycomparison with untreated controls. As shown by the test results, thecompositions according to the invention have good herbicidalpre-emergence activity against a broad spectrum of weed grasses andbroad-leaved weeds.

Scoring and evaluation of the synergistic herbicidal effects:

The herbicidal efficacy of the active compounds or active compoundmixtures was scored visually using the treated plots in comparison tountreated control plots. The damage and development of all above-groundparts of the plants were recorded. Scoring was carried out using apercentage scale (100% effect=all plants killed; 50% effect=50% of theplants and the green parts of the plants killed; 0% effect=no noticeableeffect=like control plot). The scores of in each case 4 plots wereaveraged.

When using the combinations according to the invention, herbicidaleffects on a harmful plant species are frequently observed which exceedthe formal sum of the activities of the herbicides contained in thecombination when applied on their own.

Alternatively, in some cases, it can be observed that a lowerapplication rate is required for the herbicide combination in order toobtain, compared to the individual preparations, the same effect on aharmful plant species. Such activity increases or increases ineffectiveness or reduced application rates are a strong indication of asynergistic effect.

If the observed activity values already exceed the formal sum of thevalues for the trials with the individual applications, they also exceedthe expected value according to Colby which is calculated using thefollowing formula and which is likewise considered to be an indicationof synergism (cf. S. R. Colby; in Weeds 15 (1967) pp. 20 to 22):

E=A+B−(A·B/100)

The figures denote: A, B=activity of the active compounds A or B in % ata or b g of AS/ha; E=expected value in % at a+b g of AS/ha.

The observed test results show, at suitable low dosages, an effect ofthe combinations which exceeds the expected values according to Colby.

2. Post-Emergence Effect on Weeds

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds areplaced in sandy loam soil in pots, covered with soil and grown in agreenhouse under good growth conditions (temperature, atmospherichumidity, water supply). Three weeks after sowing, the test plants aretreated at the three-leaf stage with the compositions according to theinvention. The compositions according to the invention, formulated aswettable powders or as emulsion concentrates, are sprayed, at variousdosages, onto the green parts of the plant at an application rate of 600to 800 I of water/ha (converted). After the test plants have been in thegreenhouse for about 3 to 4 weeks under ideal growth conditions, theeffect of the preparations is scored visually by comparison withuntreated controls. The compositions according to the invention alsohave a good herbicidal post-emergence activity against a broad spectrumof economically important weed grasses and weeds.

Frequently, activities of the combinations according to the inventionare observed which exceed the formal sum of the activities when theherbicides are applied individually. The observed test results show, atsuitable low dosages, an effect of the combinations which exceeds theexpected values according to Colby (cf. scoring in Example 1).

3. Herbicidal Effect and Crop Plant Compatibility (Field Trials)

Crop plants were grown outdoors on plots under natural outdoorconditions, and seeds or rhizome pieces of typical harmful plants werelaid out or the natural weed growth was utilized. Treatment with thecompositions according to the invention was carried out after theharmful plants had emerged and the crop plants were, generally, at the2- to 4-leaf stage; in some cases (as stated), application of individualactive compounds or active compound combinations was carried outpre-emergence (cf. Example 1) or as a sequential treatment partlypre-emergence and/or post-emergence.

After the application, for example 2, 4, 6 and 8 weeks after theapplication, the effect of the preparations was scored visually bycomparison with untreated controls (cf. scoring in Example 1). In thefield trial as well, the compositions according to the invention havesynergistic herbicidal activity against a broad spectrum of economicallyimportant weed grasses and broad-leaved weeds. The comparison showedthat the combinations according to the invention in most cases have ahigher, in some cases a considerably higher, herbicidal activity thanthe sum of the activities of the individual herbicides, thus indicatingsynergism. Moreover, the effects in essential phases of the scoringperiod were above the expected values according to Colby (cf. scoring inExample 1), also indicating synergism. In contrast, the crop plantswere, as a consequence of the treatments with the herbicidalcompositions, damaged only to a small degree, if at all.

SPECIFIC TEST EXAMPLES

The following abbreviations are used in the tables below:

g of AS/ha=Gram of active substance (=100% active compound) per hectare;The expected values according to Colby are in each case given inbrackets (E= . . . ).

TABLE 1 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ g of Herbicidal effect²⁾ (%) against Damage²⁾ compound(s) AS/haSEBEX AMARE (in %) to rice (A1.1)^(S) 45  0  0 0 (B4.6) 45 93 93 0(A1.1)^(S) + 45 + 45 95 95 0 (B4.6) (E = 93) (E = 93) Abbreviations forTable 1: ¹⁾= application in each case post-emergence, ²⁾= scoring 7 daysafter application (A1.1)^(S) = fenoxaprop-P-ethyl in combination withthe safener (S1-9), (S1-9) = ethyl 5,5-diphenyl-2-isoxazolinecarboxylate (B4.6) = bispyribac-Na (KIH 2023) SEBEX = Sesbania exaltata;AMARE = Amaranthus retroflexus

TABLE 2 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ g of Herbicidal effect²⁾ Damage²⁾ compound(s) AS/ha (in %)against ECHCO (in %) to rice (A1.1)  45 51 0 (83.2) 400 0 0 (A1.1) +45 + 400 56 0 (B3.2) (E = 51) Abbreviations for Table 2: ¹⁾= applicationin each case post-emergence at the 2-4-leaf stage, ²⁾= scoring 21 daysafter application (A1.1) = fenoxaprop-P-ethyl, (B3.2) = benfuresateECHCO = Echinochloa colona

TABLE 3 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ Herbicidal effect²⁾ Damage²⁾ (in %) compound(s) g of AS/ha (in %)against ECHCO to rice (A1.1) 45 83 21 (B4.9) 25 33 22 50 43 23 100  4822 (A1.1) + (B4.9) 45 + 25 95 (E = 88) 36 Abbreviations for Table 3: ¹⁾=application in each case post-emergence at he 2-4-leaf stage, ²⁾=scoring 28 days after application (A1.1) = fenoxaprop-P-ethyl, (B4.9) =oxadiargyl ECHCO = Echinochloa colona

TABLE 4 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ Herbicidal effect²⁾ Damage²⁾ (in %) compound(s) g of AS/ha (in %)against ELEIN to rice (A1.1) 45 80 21 (B4.26) 30  0 15 60 37 19 (A1.1) +(84.26) 45 + 30 96 (E = 80) 24 Abbreviations for Table 4: ¹⁾=application in each case post-emergence at the 2-4-leaf stage, ²⁾=scoring 28 days after application (A1.1) = fenoxaprop-P-ethyl, (B4.26) =maziclomefone (MY 100) ELGIN = Eleusine indica

TABLE 5 Herbicidal effect and selectivity in rice (greenhouse trial)Active Dose¹⁾ Herbicidal effect²⁾ Damage²⁾ compound(s) g of AS/ha (in %)against SAGPY (in %) to rice (A1.1) 75 0 8 37.5 0 0 (B1.15) 25 0 0 5040  0 100 80  0 (A1.1) + (B1.15) 37.5 + 50 75 (E = 40) .3 Abbreviationsfor Table 5: ¹⁾= application in each case post-emergence at the 1-2-leafstage, ²⁾= scoring 20 days after application (A1.1) =fenoxaprop-P-ethyl, (B1.15) =fentrazamid SAGPY =Sagittaria pygmaea

TABLE 6 Herbicidal effect and selectivity in rice (greenhouse trial)Active Dose¹⁾ Herbicidal effect²⁾ Damage²⁾ compound(s) g of AS/ha (in %)against ECHCG (in %) to rice (A1.1) 75 82 3 37 40 0 18 15 0 Clefoxidim(B1.31) 75 83 0 37 10 0 18  0 0 (A1.1) + (B1.31) 18 + 18 65 (E = 15) .018 + 37 85 (E = 25) .0 37 + 18 88 (E = 40) .0 Abbreviations for Table 6:¹⁾= application in each case post-emergence at the 3-4-leaf stage, ²⁾=scoring 20 days after application (A1.1) = fenoxaprop-P-ethyl, (B1.31) =clefoxidim ECHCG = Echinochloa crus-galli

TABLE 7 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ Herbicidal effect²⁾ Damage²⁾ compound(s) g of AS/ha (in %)against AMARE (in %) to rice (A1.1)^(S) 45  0 0 (B1.11) 3000 83 5(A1.1)^(S) + (B1.11) 45 + 3000 96 (E = 83) .3

TABLE 8 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ Herbicidal effect²⁾ Damage²⁾ compound(s) g of AS/ha (in %)against IPOHE (in %) to rice (A1.1)^(S) 45  0 1 (B4.25) 30 78 0(A1.1)^(S) + (B4.25) 45 + 30 90 (E = 78) .0

TABLE 9 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ Herbicidal effect²⁾ Damage²⁾ compound(s) g of AS/ha (in %)against AMARE (in %) to rice (A1.1)^(S) 60  0 4 (B3.1) 50 66 18(A1.1)^(S) + (B3.1) 60 + 50 100 (E = 96) .20

TABLE 10 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ Herbicidal effect²⁾ Damage²⁾ compound(s) g of AS/ha (in %)against SEBEX (in %) to rice (A1.1)^(S) 75  0 4 (B2.2) 32 93 13(A1.1)^(S) + (B2.2) 75 + 32 100 (E = 93) .13 Abbreviations for Tables 7,8, 9 and 10: ¹⁾= application in each case post-emergence at the 2-4-leafstage, ²⁾= scoring 28 days after application (A1.1)^(S) =fenoxaprop-P-ethyl in combination with the safener (S1-9) (S1-9) = ethyl5,5-diphenyl-2-isoxazoline carboxylate (61.11) = benthiocarb(thiobencarb) (64.25) = pyribenzoxim (B3.1) = triclopyr (B2.2) =carfentrazone ECHCG = Echinochloa crus-galli IPOHE = Ipomea hederaceaeAMARE = Amaranthus retroflexus SEBEX = Sebania exaltata

TABLE 11 Herbicidal effect and selectivity in rice (field trial)Herbicidal effect²⁾ (in %) Active Dose¹⁾ against Damage²⁾ compound(s) gof AS/ha CYPDI IPOSS (in %) to rice (A1.1)^(S) 45  0  0 27 (B4.6) 45 7591 16 (A1.1)^(S) + (B4.6) 45 + 45 89 (E = 75) 95 (E = 91) .31Abbreviations for Table 11: ¹⁾= application in each case post-emergenceat the 2-4-leaf stage, ²⁾= scoring 28 days after application (A1.1)^(S)= fenoxaprop-P-ethyl in combination with the safener (S1-9) (S1-9) =ethyl 5,5-diphenyl-2-isoxazoline carboxylate (B4.6) = bispyribac-NaCYPDI = Cyperus difformis IPOSS = Ipomoea spp

TABLE 12 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ Herbicidal effect²⁾ Damage²⁾ compound(s) g of AS/ha (in %)against ECHCG (in %) to rice (A1.1) 80 97 5 40 95 0 20 80 0 (B1.7) 500030 5 2500 10 5 1250  0 0 (A1.1) + (B1.7) 20 + 1250 93 (E = 80) 0 20 +2500 98 (E = 90) 3 Abbreviations for Table 12: ¹⁾= application in eachcase post-emergence at the 3-leaf stage, ²⁾= scoring 12 days afterapplication (A1.1) = fenoxaprop-P-ethyl (B1.7) = propanil ECHCG =Echinochloa crus-galli

TABLE 13 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ Herbicidal effect²⁾ Damage²⁾ compound(s) g of AS/ha (in %)against ECHCG (in %) to rice (A1.1)^(S) 20 75 0 (B2.4) 37.5  0 0(A1.1)^(S) + (B2.4) 20 + 37.5 85 (E = 75) 0 Abbreviations for Table 13:¹⁾= application in each case post-emergence at the 1-2-leaf stage, ²⁾=scoring 28 days after application (A1.1)^(S) = fenoxaprop-P-ethyl incombination with the safener (S1-9), (S1-9) = ethyl5,5-diphenyl-2-isoxazoline carboxylate (B2.4) = tritosulfuron ECHCG =Echinochloa crus-galli

TABLE 14 Herbicidal effect and selectivity in rice (field trial) ActiveDose¹⁾ Herbicidal effect²⁾ Damage²⁾ compound(s) g of AS/ha (in %)against CYPIR (in %) to rice (A1.1)^(S) 60  0 0 75  0 0 (B4.2) 300 30 0(A1.1)^(S) + (B4.2) 75 + 300  50 (E = 30) 0 (B4.8) 250 75 0 (A1.1)^(S) +(B4.8) 75 + 250  82 (E = 75) 0 (B1.11) 1500 78 0 (A1.1)^(S) + (B1.11)75 + 1500 82 (E = 78) 0 Abbreviations for Table 14: ¹⁾= application ineach case post-emergence at the 3-leaf stage, ²⁾= scoring 42 days afterapplication (A1.1)^(S) = fenoxaprop-P-ethyl in combination with thesafener (S1-9), (S1-9) = ethyl 5,5-diphenyl-2-isoxazoline carboxylate(B4.2) = clomazone (B4.8) = oxadiazon (B1.11) = thiobencarb CYPIR =Cyperus iria

1-15. (canceled)
 16. A herbicide-combination comprising: a herbicidallyeffective content of a synergistic combination of (A) fenoxaprop-P-ethyland (B) propanil; wherein the ratio by weight of (A):(B) is 50:1 to1:200.
 17. The herbicide combination according to claim 16; wherein theratio by weight of (A):(B) is 5:1 to 1:200.
 18. The herbicidecombination according to claim 16; wherein the ratio by weight of(A):(B) is 5:2 to 1:200.
 19. A method for controlling harmful plants,which comprises: applying a synergistic combination of (A)fenoxaprop-P-ethyl and (B) propanil; wherein the ratio by weight of(A):(B) is 50:1 to 1:200.
 20. The method according to claim 19; whereinthe ratio by weight of (A):(B) is 5:1 to 1:200.
 21. The method accordingto claim 19; wherein the ratio by weight of (A):(B) is 5:2 to 1:200. 22.The method according to claims 19; wherein (A) 5 to 500 g a.i./hafenoxaprop-P-ethyl and (B) 10 to 4000 g a.i./ha propanil are applied.23. The method according to claims 20; wherein (A) 5 to 500 g a.i./hafenoxaprop-P-ethyl and (B) 10 to 4000 g a.i./ha propanil are applied.24. The method according to claims 21; wherein (A) 5 to 500 g a.i./hafenoxaprop-P-ethyl and (B) 10 to 4000 g a.i./ha propanil are applied.25. The method according to one of claims 19-24; wherein the weeds arecontrolled in a rice crop.